Process of preparing compounds of azoproteins with antimony



6 pounds of azoproteins with antimony have, howwith 10 cc. of 2N-solution of sodium carbonate 6 Patented Aug. 23, 1938 2 l UNITED STATES PATENT OTFFlC-E PROCESS OF PREPARING COMPOUNDS 0F AZOPROTEINS WITH AN TIMON Y Max Bockmiihl, Willy Ludwig, and Paul von Mutzenbecher, Frankfort-on-the-Main-Hochst, Germany, assignors to Winthrop Chemical Company, Inc., New York, N. Y., a corporation of New York No Drawing. Application August 18, 1936, Se-

rial No. 96,699. In Germany December 7,

3 Claims. (01. 260-113) The present invention relates to a process of tered from the undissolved antimony trioxide, preparing compounds of azoproteins with antiacidified with hydrochloric acid and diazotized, mony. while cooling with ice, by means of a solution of Azoproteins have already been prepared; comsodium nitrite. 25 cc. of horse serum are mixed ever, hitherto been unknown. According tothis and the diazonium solution is added. After 3 invention these new compounds can be obtained hours the azoprotein is precipitated with an acid, by diazotizing an antimony compound of an arodissolved in dilute caustic soda solution and diamatic amine and coupling the diazotized product lyzed against distilled water. The solution which with albumin or by subsequently introducing the after the dialysis is concentrated to 60 cc. conantimony into an azoprotein. tains 2.5 per cent of dry substance and 0.012

As albumin component there may be used p C t of n yserum, the serum fractions, casein, etc. (3) Serum protein-4-azo-2-chlorobenzene-1- The resultant antimony compounds of the azostlbonic acid.

proteins possess valuable chemo-therapeutic 3.6 grams of 4-acetylamino-2-chlorobenzene-1- properties. stibonic acid are mixed with 50 cc. of a 1.5N-

The following examples illustrate the inven- Caust c S a 80111131011. p for hour 011 3 tion: j i steam bath at a temperature of 90 C. until the (1) Antimony compound of tartranilic cid solution has become clear; it is then cooled, coupled with serum. mixed with an excess of hydrochloric acid and 3 grams of tartranilic acid of the f ll wi g diazotized, while cooling with ice, with 100 cc. of composition a N/10-solution of sodium nitrite. 250 cc. of serum are mixed with 100 cc. of a ZN-solution of H.N-NHO0CHoH-c00n sodium carbonate and the diazonium solution is OH H gradually added while strongly stirring. The according to Landsteiner (J our. eXp. Med. 50, g g gggg 1s obtamed as yellow-red gramy pre- 1929, page 408) are dissolved in a mixture of 100 cc. of water and 35 cc. of hydrochloric acid of 10 per cent strength, the solution is diazotized with 100 cc. of a N/10 sodium nitrite solution and made up with ice water to 500 cc. 250 cc. of horse serum are mixed with 50 cc. of a sodium carbonate solution of 10 per cent strength and then, while cooling with ice, at first with of the dilute diazotate solution. After 1 hours the remaining is added and the whole allowed to stand for 1 hour. During all the time the reaction is kept feebly positive to phenolphthalein with a solution of sodium carbonate. An acid is then added and the precipitate thus produced is centrifuged, dissolved in dilute caustic soda solution and dialyzed in the Cellophane tube, until (4) Antimony compound of casein-azo-tartranilic acid.

3 grams of tartranilic acid are dissolved in a mixture of 100 cc. of water and cc. of hydrochloric acid of 10 per cent strength; the solution is diazotized with a N /10-solution of sodium nitrite and made up with ice water to 500 cc. 15 grams of casein are dissolved in 300 cc. of a 3 per 35 cent solution of sodium carbonate and then, while cooling with ice, at first mixed with 300 cc. of the diazotate solution. After 1 hours the remaining part is added and the whole allowed to stand in ice for 1 hour, the reaction being kept feebly positive to phenolphthalein. The precipitation by m'eans of acid, the dialysis and the inthe chlorine ions disappear in the outer water. trodqction. of the antimony are carried as 70 cc. of this 8 per cent solution are mixed with descnbed m Example. r 35 cc. of a 10 per cent solution of sodium car- (5) Serum albumm'li'azo'z chlorobenzene'1' J bonate and a solution of 0.5 gram of antimony stibomc acidtrioxide in 8 cc. of IN-hydrochloric acid is added Sawmill-cation of the c t l compound of drop by drop. The solution is then again rem the free acid and the diazotization are carried out dered feebly alkaline and dialyzed in order to as describedin EXample The d a on um solucompletely purify it. tion is gradually added to 300 cc. of a 5 per cent (2) 0.3 gram of tartranilic acid is dissolved in solution of serum albumin which contains 10 water, neutralized with caustic soda solution and grams of anhydrous sodium carbonate. When boiled for some time with 0.3 gram of antimony the coupling is finished the azoprotein is precipitrioxide. The supernatant solution is now filtated with the aid of an acid.

We claim:

1. Process of preparing compounds from azoproteins and antimony which comprises diazotizing an amine of the benzene series, coupling the diazotate with albumin and causing the product thus obtained to react with an antimony compound.

2. Process of proteins and antimony which comprises diazotizing an amine of the benzene series, coupling the diazotate with serum and causing the product thus obtained to react with an antimony compound.

preparing compounds from azo- 3. Process of preparing compounds from azoproteins and antimony which comprises diazotizing an acid of the formula OH OH coupling the diazotate with horse serum and causing the product thus obtained to react with antimony trioxide.

MAX BocKMiiHL.

WILLY LUDWIG.

PAUL vou MU'IZENBECHER. 

